Preparation of resins from c5 fractions and cyclopentadiene dimers



United States Patent PREPARATION OF RESINS FROM C FRACTIONS ANDCYCLOPENTADIENE DIMERS Robert F. Leary, Cranford, N. J., assignor toEsso Research and Engineering Company, a corporation of Delaware N0Drawing. Application July 3, 1953, Serial No. 366,061

2 Claims. (Cl. 260-82)- This invention is concerned with thepreparationof high quality resins by the Friedel-Crafts polymerizationof selected fractions of steam-cracked petroleum streams,

and more particularly, with the improvement of resins 1 kerosene, gasoil, and the like, are cracked at relatively low pressures and attemperatures of 1000 to 1600" F. in the presence of steam and forrelatively short contact times. The gas and liquid streams producedcontain large quantities of diolefins and olefins in the C5 to C10range. The naphtha distillate streams obtained by these steam crackingoperations contain relatively large amounts of diolefins, olefins,aromatics, and some paraflins.

The process of this invention involves the selection and polymerizationof blends prepared from a C5 fraction of olefins boiling below about 38C. together with critical amounts of cyclopentadienes.

To obtain the selected and preferred polymen'zation feed streams to' beused" in this invention, the streams containing C5 olefins are initiallyprocessed to remove the isoprene, piperylene and cyclopentadienes. Thecyclopentadienes are removed as dimers. The chief components includecyclopentadiene dimer and methyl cyclopentadiene dimer, and the codimer.

By an initialthermal soaking of'the" C5 to C8 or C9 fraction boilingfrom the initial boiling point up toabout 140 C. withsufl'icientheatingtime, the cyclope'ntadienes are dimerized andseparated by careful vacuum or steam distillation. Preferred dimerizing,temperatures are in the range of 100220 F. The dimers are removed as abottoms fraction from the distillation tower, the tower being operatedto prevent any substantial depolymerization of the cyclopentadiene's. Inthis distillation, the C5-C8 hydrocarbons boiling below the' dimers areremoved as an overhead distillate stream.

The overhead is then refractionated to obtain a cut boiling up to about38 C., which will contain the isoprene, a very small amount ofpiperylene, and the lower boiling C5 olefins. This step separates mostof the piperylene and the higher boiling C5 olefins, together with C toC3 compounds, as the distillation-bottoms. A suitable extraction process(e. g. extractive distillation with acetone) appliedto the I. B. P.38 C.fraction'removes and recovers the isoprene and usually the small amountof piperylene, leaving a raffinate which contains principally the lowerboilinggCs olefins.

The total C5 fraction in the original C5-140 C. cut has the followinggeneral composition:

Component: Wt. percent isoprene 1-2-18 Cyclopentadiene 12-18 Piperylene15-10 Other diolefins 1-2 Branched chain olefins a 18-23 Normal olefins20-28 Cyclic olefins 4-6 Paraflins 1-3 2 After removal of isoprene,piperylene, and higher boilingcomponents, the I. B. P. to 38 C. fractionhas the following general composition:

This fraction is then mixed with 10 to 50 wt. percent of cyclopentadienedimers before the polymerization step. The resulting blends arepolymerized with a Friedel- Crafts catalyst, for example, the aluminumhalide catalysts. Aluminum chloride and aluminum bromide arequite-satisfactory.

Without the cyclopentadiene dimers being present, the C5 fraction, uponpolymerization,- gives low molecular weight, oily polymers of little orno value.

By operating. according. to this invention, resins of higher softeningpoints and good color qualities can be prepared by including. in *theunsaturated stream above 10% up to 50% of dicyclopentadiene,di-methylcycl-opentadi'ene, or di-Cq-cyclopentadienes, codimers,mixtures of dimers, or concentrates thereof, based on the amount oftotal hydrocarbon feed.

It is preferable to add thegcyclopentadienes to the feed:

as the dimers rather than as the monomers, since the monomers whenpresent in any appreciable concentration in the polymerization reactionmixture, tend to give prod= ducts containing insoluble, gelled polymer.This tendency to give gel can be reduced by adding the, cyclopentadienemonomer to the reaction mixture after; the catalyst is added, or bycarrying outthe reaction in a continuous fashion. In the latter case,feed and catalyst are added to an agitated vessel, from which theproduct overflows. The concentration of active monomers in the vessel islow at all times, and it has been found that'the tendency to form gel istherefore reduced.

As a convenient source of the dimers, thecycl-opentadiones can beconverted to dimers by thermal soaking, following which the total soakedstream is subjected to distillation under conditions whereby thecycl'op'entadiene dimers are maintained in the dimerized form, and areseparated as a'residue. The dimers are then blended with the C5 cut. Ifdesired, selective port-ions (i. e.

C5 or C6 cyclopentadienes) of the cyclopentadien'es are.

out at temperatures of 20 upto90" C., preferably 0 to- C.

The polymerization reaction is carried out as a liquid phase operation.The catalyst may be added continually or batchwise. Any practical andeffective methods for adding catalyst and reactants-can be utilized.

The time required to carry out the polymerization .de-

pends primarily on the rate that the catalyst can be added such that thereaction can be adequately controlled. The

products are worked upby water or caustic washing. or by washingwithdilute H2804 (5%) followed by Water washing. The catalyst residues canalso be removed by precipitation as'a methanol catalyst complex followedby subsequent filtration. The polymerized resin is then stripped free ofunreacted feed components and any of the low molecular Weightpolymerization products to give the final oil or resin. The exact yieldand softening point of the final product will depend on the degree ofstripping.

These solid resins can be used as a base for paint, in formulations forfloor tile and the like, for varnish manu- Patented Dec. 4, 1956facture, or formulated into printing ink. The resin has The aboveresults 'show that the C5 fraction when a good color and odor and ismiscible in a naphtha polymerized alone, gives not resins, but veryviscous oils olv t of low value.

Typical examples of the invention are set forth below, EXAMPLE 2although it is not intended to limit the invention in any 5 Ano her sries f r w carried out using various way t th ti l experiments Presentefeed mixtures. The conditions of the experiments and the resultsobtained thereby are shown in Table II. The EXAMPLE 1 data show thatcyclopentadiene monomers can be utilized as well as dimers, but thatprecautions should be taken A typical fraction used in the followingblends with 10 against gel formation with the monomers.

Table 11 Wt. Percent of Feed 7 Resin Run No. Feed Composition CatalystResin Fill Ma- Gel Soft. Pt., C. Color Iodine terial No.

807 o. v 6 20%? Methylcyclopentadiene Dimer. k A1013 113's 8 211 7 3 7;cyclopentadiene Dimer 1 1-0 A1013 2 -6 2' 3 180 5 8 gyclopentadieneMonomer LG U013 23 2 be 2 v t 1.0 A10]; in Ethyl 18.0 25.2 s9.o. s 180 97 Cyclopentadiene Monomer (ii-hexane diluent). Chloride 1 Run at 35 0.,the reflux point. Other runs made at 20 C.

2 Added after AlCl; catalyst. 3 Resin gels on heating.

the cyclopentadiene dimers contains the following EXAMPLE 3 components:pentenedl The data in Table III show that AlBrs is an eifective Cis andtrans pentene 2 catalyst, and that a wide range of reaction temperaturesZ-methyl-l-butene can be employed 2-methyl-2- butene 3-methyl-1-buteneTable III n-Pentane i P 7, [Reactions with 80% C5-20% cyclopentadienedimer feed] and very small amounts of Wt.P t R in g g plpewlene mm...Yar 52%..

3'6 Open in? 0 Reaction Temp., 0. Catalyst Pt., Cyclopentadiene R in FmCyclopentane es The above fraction having a boiling range from about 01% A10], m6 1&6 61 5 20 up to 38 C. was then blended with varyingamounts 1% AlBn 15.7 12.7 59 0 of a dimer fraction having about 40%cyclopentadiene 05% Aloh'm 67 0 dimer and about 35%methylcyclopentadiene dimer and the resulting blends subjected topolymerization with Feed diluted with equal 701111119 ofn'heptane- AlClscatalyst at 20-30 C. The excess catalyst was removed by caustic andwater washing prior to distillation step to recover the resin formed.The data obtained are 50 What is claimed is:

tabulated in Tablelbelow' l. A process for preparing soluble petroleumresins Table I which comprises blending a C5 steam-cracked petroleumfraction relatively free of cyclopentadienes and dimers A101; Wt.PercentYield thereof and isoprene and boiling up to 38 C. with from RNln Feedgggi osigategrst, m Z 10-50 Wt. percent of cyclopen-tadiene dimers,subjecting V erof Resin, C.

cent Resin Fill Mathe resulting blend to polymerization at temperaturesof term from 20 to +90 C. in the presence of aluminum halide andisolating the resin produced thereby. 92%; gf 2. Process according toclaim 1 in which the catalyst ture. is aluminumchloride and thetemperature is maintained 5131:: 'iintis:::::::: 3:3 i333 riff). 150.atbetweeno and 4 St 2.0 37.5 9.5 130. 5 0 3&3 8'2 94' References Citedin the file of this patent 65 UNITED STATES PATENTSsmfigftitfitifrtsliifitlit fieifittiiigfii x25 mm M .7 Thom 4 1 N0dimers added. 2,521,022 Rowland Sept. 5, 1950

1. A PROCESS FOR PREPARING SOLUBLE PETROLEUM RESINS WHICH COMPRISESBLENDING A C5 STEAM-CRACKED PETROLEUM FRACTION RELATIVELY FREE OFCYCLOPENTADIENES AND DIMERS THEREOF AND ISOPRENE AND BOILING UP TO 38*C. WITH FROM 10-50 WT. PERCENT OF CYCLOPENTADIENE DIMERS, SUBJECTING THERESULTING BLEND TO POLYMERIZATION AT TEMPERATURES OF FROM -20 TO +90* C.IN THE PRESENCE OF ALUMINUM HALIDE AND ISOLATING THE RESIN PRODUCEDTHEREBY.